A comparison of the molecular orbital (ab initio, CNDO and EHT) methods applied to the conformational study of thiocarbonohydrazide in its basic and diprotonated forms

Conformational preferences of thiocarbonohydrazide (H2NNHCSNHNH2) in its basic and N,N′-diprotonated forms are examined by calculating the barrier to internal rotation around the C---N bonds, using the theoretical LCAO—MO (ab initio and semiempirical CNDO and EHT) methods. The calculated and experimental results are compared with each other and also with values for N,N′-dimethylthiourea which is isoelectronic with thiocarbonohydrazide. The suitability of these methods for studying rotational isomerism seems suspect when lone pair interactions are present.

Short-window spectral analysis using AMVAR and multitaper methods: a comparison

We compare two popular methods for estimating the power spectrum from short data windows, namely the adaptive multivariate autoregressive (AMVAR) method and the multitaper method. By analyzing a simulated signal (embedded in a background Ornstein-Uhlenbeck noise process) we demonstrate that the AMVAR method performs better at detecting short bursts of oscillations compared to the multitaper method. However, both methods are immune to jitter in the temporal location of the signal. We also show that coherence can still be detected in noisy bivariate time series data by the AMVAR method even if the individual power spectra fail to show any peaks. Finally, using data from two monkeys performing a visuomotor pattern discrimination task, we demonstrate that the AMVAR method is better able to determine the termination of the beta oscillations when compared to the multitaper method.

Dihydrofolate reductase from soybean seedlings: A fluorescence and circular dichroism study

The fluorescence emission spectrum of soybean dihydrofolate reductase suggests that the emitting tryptophan residues are situated in a hydrophobic microenvironment. The dissociation constants determined from fluorescence and circular dichroism data reveal that the soybean enzyme has a lower affinity for substrates and substrate analogs than that determined for dihydrofolate reductases isolated from other sources. The binding of methotrexate to the soybean enzyme does not affect the binding of NADPH. Similarly, the binding of NADPH has no effect on subsequent methotrexate binding. Polarimetric study indicates that the enzyme has a low (ca. 5%) α-helical content. Addition of dihydrofolate to the soybean enzyme results in the generation of a positive ellipticity band at 298 nm with a molar ellipticity, [θ], of 186,000, whereas the binding of folate induces a negative ellipticity band at 280 nm with [θ] of −181,000. The qualitative and quantitative differences in the circular dichroism of the enzyme-dihydrofolate and enzyme-folate complexes indicate that the mode of binding of these ligands may be different. The formation of an enzyme-NADPH complex is accompanied by a negative Cotton effect at 270 nm. These studies indicate that the binding of substrates or inhibitors causes significant conformational changes in the enzyme and also leads to the formation of a number of spectroscopically identifiable complexes.

Fungal flora of rice field soils

Qualitative and quantitative assessment of the fungal flora of rice field soils yielded 102 species of fungi belonging to 44 genera, when dilution plate, soil plate, root-washing and baiting techniques were employed. The order of efficacy of the methods used was: root-washing > soil plate > dilution plate > baiting. Baiting method, used specifically to isolate aquatic and keratinophilic fungi from soils was studied in detail with reference to the former. Qualitatively, corn leaf bait was the most efficient one while pine pollens and hemp seeds were least efficient. A semi-quantitative method was employed to study the statistically significant differences among the different factors used. Among the keratinophilic baits,viz., human hair, fowl’s feather and wool, wool bait was least efficient. The results of this investigation are discussed.

Carotenoids In 3 Stages Of Ripening Of Mango

The distribution of carotenoids, both qualitative and quantitative, during 3 stages of ripening of mango has been studied using chromatographic, spectroscopic and chemical methods. There was an increase in content as well as in number of carotenoids during ripening. The present study showed there were 15, 14 and 17 different carotenoids in the unripe, partially ripe and fully ripe mangoes, respectively. Even though phytofluene (39.26%) was the major carotenoid in the partially ripe mango, β-carotene constituted the major carotenoid in the unripe (37.47%) and fully ripe mango (50.64%). cis-β-Carotene was present only in the fully ripe mango. Only the unripe mango contained ζ-carotene, whereas γ-carotene was present in all the 3 stages of ripening. The major xanthophyll present in the unripe mango was mutatoxanthin (9.44%), whereas auroxanthin constituted the major hydroxylated carotenoid of the partially ripe (5.07%) and fully ripe (10.40%) mangoes. The percent of cryptoxanthin dropped to lower levels during ripening. As ripening proceeded, lutein completely is appeared. There were significant quantities of eaxanthin in the partially ripe and fully ripe mango. Epoxy carotenoids such as 5,6-monoepoxy-β-carotene, mutatochrome, cis-violaxanthin, luteoxanthin, mutatoxanthin and auroxanthin were observed in all 3 stages of ripening.

Isolation and characterization of a naturally occurring inhibitor from mung bean (Vigna radiata) seedlings for serine hydroxymethyltransferase

A naturally occurring inhibitor of serine hydroxymethyltransferase (EC2.1.2.1) in mung bean seedlings extracts was purified by ammonium sulphate precipitation, phenyl-Sepharose chromatography followed by heating to release the inhibitor bound to the protein. The inhibitor had an absorption maximum at 200 nm, was not precipitated by trichloroacetic acid, was dialysable and resistant to inactivation by heating at 98-degrees-C for 4 hr, protease and ribonuclease digestion; but was acid labile. The chromatographically pure preparation inhibited both mung bean and sheep liver SHMT. Qualitative and quantitative analyses indicated that it contained a carbohydrate moiety, an O-amino and vicinal diol groups. Paper electrophoresis at pH 4.3 suggested that the inhibitor was positively charged.

Comparative study of different formulations and solution methods for two phase flow in saturated porous media

Six models (Simulators) are formulated and developed with all possible combinations of pressure and saturation of the phases as primary variables. A comparative study between six simulators with two numerical methods, conventional simultaneous and modified sequential methods are carried out. The results of the numerical models are compared with the laboratory experimental results to study the accuracy of the model especially in heterogeneous porous media. From the study it is observed that the simulator using pressure and saturation of the wetting fluid (PW, SW formulation) is the best among the models tested. Many simulators with nonwetting phase as one of the primary variables did not converge when used along with simultaneous method. Based on simulator 1 (PW, SW formulation), a comparison of different solution methods such as simultaneous method, modified sequential and adaptive solution modified sequential method are carried out on 4 test problems including heterogeneous and randomly heterogeneous problems. It is found that the modified sequential and adaptive solution modified sequential methods could save the memory by half and as also the CPU time required by these methods is very less when compared with that using simultaneous method. It is also found that the simulator with PNW and PW as the primary variable which had problem of convergence using the simultaneous method, converged using both the modified sequential method and also using adaptive solution modified sequential method. The present study indicates that pressure and saturation formulation along with adaptive solution modified sequential method is the best among the different simulators and methods tested.

Estimation of groundwater recharge of shallow aquifer on humid environment in Yaounde, Cameroon using hybrid water-fluctuation and hydrochemistry methods

A study of environmental chloride and groundwater balance has been carried out in order to estimate their relative value for measuring average groundwater recharge under a humid climatic environment with a relatively shallow water table. The hybrid water fluctuation method allowed the split of the hydrologic year into two seasons of recharge (wet season) and no recharge (dry season) to appraise specific yield during the dry season and, second, to estimate recharge from the water table rise during the wet season. This well elaborated and suitable method has then been used as a standard to assess the effectiveness of the chloride method under forest humid climatic environment. Effective specific yield of 0.08 was obtained for the study area. It reflects an effective basin-wide process and is insensitive to local heterogeneities in the aquifer system. The hybrid water fluctuation method gives an average recharge value of 87.14 mm/year at the basin scale, which represents 5.7% of the annual rainfall. Recharge value estimated based on the chloride method varies between 16.24 and 236.95 mm/year with an average value of 108.45 mm/year. It represents 7% of the mean annual precipitation. The discrepancy observed between recharge value estimated by the hybrid water fluctuation and the chloride mass balance methods appears to be very important, which could imply the ineffectiveness of the chloride mass balance method for this present humid environment.

Comparative Assessment of Techniques for Bioresource Monitoring Using GIS and Remote Sensing

Growing concern over the status of global and regional bioenergy resources has necessitated the analysis and monitoring of land cover and land use parameters on spatial and temporal scales. The knowledge of land cover and land use is very important in understanding natural resources utilization, conversion and management. Land cover, land use intensity and land use diversity are land quality indicators for sustainable land management. Optimal management of resources aids in maintaining the ecosystem balance and thereby ensures the sustainable development of a region. Thus sustainable development of a region requires a synoptic ecosystem approach in the management of natural resources that relates to the dynamics of natural variability and the effects of human intervention on key indicators of biodiversity and productivity. Spatial and temporal tools such as remote sensing (RS), geographic information system (GIS) and global positioning system (GPS) provide spatial and attribute data at regular intervals with functionalities of a decision support system aid in visualisation, querying, analysis, etc., which would aid in sustainable management of natural resources. Remote sensing data and GIS technologies play an important role in spatially evaluating bioresource availability and demand. This paper explores various land cover and land use techniques that could be used for bioresources monitoring considering the spatial data of Kolar district, Karnataka state, India. Slope and distance based vegetation indices are computed for qualitative and quantitative assessment of land cover using remote spectral measurements. Differentscale mapping of land use pattern in Kolar district is done using supervised classification approaches. Slope based vegetation indices show area under vegetation range from 47.65 % to 49.05% while distance based vegetation indices shoes its range from 40.40% to 47.41%. Land use analyses using maximum likelihood classifier indicate that 46.69% is agricultural land, 42.33% is wasteland (barren land), 4.62% is built up, 3.07% of plantation, 2.77% natural forest and 0.53% water bodies. The comparative analysis of various classifiers, indicate that the Gaussian maximum likelihood classifier has least errors. The computation of talukwise bioresource status shows that Chikballapur Taluk has better availability of resources compared to other taluks in the district.

Simple and efficient methods for discrimination of chiral diacids and chiral alpha-methyl amines

The three-component chiral derivatization protocols have been developed for H-1, C-13 and F-19 NMR spectroscopic discrimination of chiral diacids by their coordination and self-assembly with optically active (R)-alpha-methylbenzylamine and 2-formylphenylboronic acid or 3-fluoro-2-formylmethylboronic acid. These protocols yield a mixture of diastereomeric imino-boronate esters which are identified by the well-resolved diastereotopic peaks with significant chemical shift differences ranging up to 0.6 and 2.1 ppm in their corresponding H-1 and F-19 NMR spectra, without any racemization or kinetic resolution, thereby enabling the determination of enantiopurity. A protocol has also been developed for discrimination of chiral alpha-methyl amines, using optically pure trans-1,2-cyclohexanedicarboxylic acid in combination with 2-formylphenylboronic acid or 3-fluoro-2-fluoromethylboronic acid. The proposed strategies have been demonstrated on large number of chiral diacids and chiral alpha-methyl amines.

Electronic structure of Nd1-xYxMnO3 from Mn K edge absorption spectroscopy and DFT methods

The electronic structure of Nd1-xYxMnO3 (x-0-0.5) is studied using x-ray absorption near-edge structure (XANES) spectroscopy at the Mn K-edge along with the DFT-based LSDA+U and real space cluster calculations. The main edge of the spectra does not show any variation with doping. The pre-edge shows two distinct features which appear well-separated with doping. The intensity of the pre-edge decreases with doping. The theoretical XANES were calculated using real space multiple scattering methods which reproduces the entire experimental spectra at the main edge as well as the pre-edge. Density functional theory calculations are used to obtain the Mn 4p, Mn 3d and O 2p density of states. For x=0, the site-projected density of states at 1.7 eV above Fermi energy shows a singular peak of unoccupied e(g) (spin-up) states which is hybridized Mn 4p and O 2p states. For x=0.5, this feature develops at a higher energy and is highly delocalized and overlaps with the 3d spin-down states which changes the pre-edge intensity. The Mn 4p DOS for both compositions, show considerable difference between the individual p(x), p(y) and p(z)), states. For x=0.5, there is a considerable change in the 4p orbital polarization suggesting changes in the Jahn-Teller effect with doping. (C) 2013 Elsevier Ltd. All rights reserved.

Giant actuation in bulk carbon nanotubes under coupled electric and magnetic fields

We report an enhanced actuation in bulk carbon nanotubes (CNTs) under coupled electric and magnetic fields, which is much higher than that evaluated in the presence of individual fields. Coupled electric and magnetic fields induce a directional actuation demonstrating a transformation from polarity independent to dependent actuation behavior of CNTs. Both qualitative and quantitative analyses are performed to understand this transformation in the bulk CNTs. Moreover, actuations along radial and axial directions of CNTs have also demonstrated a similar directional behavior.

Phase diagram of the half-filled ionic Hubbard model

We study the phase diagram of the ionic Hubbard model (IHM) at half filling on a Bethe lattice of infinite connectivity using dynamical mean-field theory (DMFT), with two impurity solvers, namely, iterated perturbation theory (IPT) and continuous time quantum Monte Carlo (CTQMC). The physics of the IHM is governed by the competition between the staggered ionic potential Delta and the on-site Hubbard U. We find that for a finite Delta and at zero temperature, long-range antiferromagnetic (AFM) order sets in beyond a threshold U = U-AF via a first-order phase transition. For U smaller than U-AF the system is a correlated band insulator. Both methods show a clear evidence for a quantum transition to a half-metal (HM) phase just after the AFM order is turned on, followed by the formation of an AFM insulator on further increasing U. We show that the results obtained within both methods have good qualitative and quantitative consistency in the intermediate-to-strong-coupling regime at zero temperature as well as at finite temperature. On increasing the temperature, the AFM order is lost via a first-order phase transition at a transition temperature T-AF(U,Delta) or, equivalently, on decreasing U below U-AF(T,Delta)], within both methods, for weak to intermediate values of U/t. In the strongly correlated regime, where the effective low-energy Hamiltonian is the Heisenberg model, IPT is unable to capture the thermal (Neel) transition from the AFM phase to the paramagnetic phase, but the CTQMC does. At a finite temperature T, DMFT + CTQMC shows a second phase transition (not seen within DMFT + IPT) on increasing U beyond U-AF. At U-N > U-AF, when the Neel temperature T-N for the effective Heisenberg model becomes lower than T, the AFM order is lost via a second-order transition. For U >> Delta, T-N similar to t(2)/U(1 - x(2)), where x = 2 Delta/U and thus T-N increases with increase in Delta/U. In the three-dimensional parameter space of (U/t, T/t, and Delta/t), as T increases, the surface of first-order transition at U-AF(T,Delta) and that of the second-order transition at U-N(T,Delta) approach each other, shrinking the range over which the AFM order is stable. There is a line of tricritical points that separates the surfaces of first- and second-order phase transitions.

Biocompatibility property of 100% strontium-substituted SiO2-Al2O3-P2O5-CaO-CaF2 glass ceramics over 26 weeks implantation in rabbit model: Histology and micro-Computed Tomography analysis

One of the desired properties for any new biomaterial composition is its long-term stability in a suitable animal model and such property cannot be appropriately assessed by performing short-term implantation studies. While hydroxyapatite (HA) or bioglass coated metallic biomaterials are being investigated for in vivo biocompatibility properties, such study is not extensively being pursued for bulk glass ceramics. In view of their inherent brittle nature, the implant stability as well as impact of long-term release of metallic ions on bone regeneration have been a major concern. In this perspective, the present article reports the results of the in vivo implantation experiments carried out using 100% strontium (Sr)-substituted glass ceramics with the nominal composition of 4.5 SiO2-3Al(2)O(3)-1.5P(2)O(5)-3SrO-2SrF(2) for 26 weeks in cylindrical bone defects in rabbit model. The combination of histological and micro-computed tomography analysis provided a qualitative and quantitative understanding of the bone regeneration around the glass ceramic implants in comparison to the highly bioactive HA bioglass implants (control). The sequential polychrome labeling of bone during in vivo osseointegration using three fluorochromes followed by fluorescence microscopy observation confirmed homogeneous bone formation around the test implants. The results of the present study unequivocally confirm the long-term implant stability as well as osteoconductive property of 100% Sr-substituted glass ceramics, which is comparable to that of a known bioactive implant, that is, HA-based bioglass. (c) 2014 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 103B: 1168-1179, 2015.